Anhydro amides



UnitediStates Patent 2,993,887 7 AN'HYDRO MIDES John D. Zech,Wilmington, Del., assignor to Atlas Powder Company, Wilmington, Del., acorporation of Delaware No Drawing. Filed Jan. 6, 1953, Ser. No. 329,9218 Claims. (Cl. 260-211) R is the residue of an anhydridized hexanepentol R is a monovalent hydrocarbon radical R is the hydrocarbonresidue of a carboxylic acid having from 2 to 25 carbon atoms Thecompounds of the present invention are prepared by the reaction of aproduct from the reduction of a monosaccharide in the presence of asuitable primary amine with an organic carboxylic acid. Such productsare identified as hexityl amines. Suitable hexityl amines include, butare not limited to, such amines as N-methyl glucamine, N-ethylglucamine, N-butyl glucamine, N-phenyl glucamine, N-hydroxy' ethylglucamine, N-cyclo hexyl glucamine, N-benzyl glucamine,. N-laurylglucamine, N- cetyl glucamine, N-octadecyl glucamine, N-allyl glucamine,N-methyl fructamine, N-ethyl fructamine, etc. Suitable carboxylic acidsinclude, but are not limited to, such carboxylic acids as acetic,caproic, capric, lauric, myristic, palmitic, oleic, stearic, linoleic,linolenic, eleostearic, behenic, benzoic, p-tertiary butyl benzoic,phenyl acetic, phenoxy acetic, 2,4-dichlorophenoxy acetic, 2,4,-

S-trichloro-phenoxy acetic, glycollic, lactic, ricinoleic,chloro-acetic, tall oil, cottonseed oil fatty acids, rosin, coconut oilfatty acids, etc.

When carboxylic acids are reacted with hexityl amines at temperatures inthe range of about 180 to about 200 C., heterocyclic amides are formedthrough the elimination of two or more moles of water per mole ofcarboxylic .acid reacted with an equivalent amount of hexityl amine. Theidentity of the hexityl amine is lost, inasmuch as the heterocyclic ringstructures that are formed as the result of anhydridization differmarkedly from the structural configuration of the hexityl amine. Whilethe exact structure of these heterocyclic amides has not been definitelyestablished, there are several possibilities to be considered intheorizing as to the possible structure of these heterocyclic rings. Itis to be understood that applicant neither intends nor desires to bebound by this explanation, but offers it only to explain the possiblenature of the compounds covered by this invention. It seems from presentinvestigation that the heterocyclic amides in question may be eithermonocyclic or dicyclic ring structures. Some possibilities are asfollows:

CNg-HOH Patented July 25,1961

. O m-Nil-R,

to 220 0., preferably at temperatures of 180 C. to

200 C. until two or more moles of water have been eliminated. An inertgas may be used to facilitate the removal of water and also to protectthe reactants from atmospheric oxidation. When a fatty carboxylic acidis 'mixed with a hexityl amine, a soap is formed which has a highviscosity at temperatures below C. To avoid this, it is often desirableto have both reactants preheated to about 150 to C. before mixing.Following the preheating of the reactants, they are then admixed and thetemperatureraised to the desired reaction temperature as indicatedabove. In the early part of the reaction it is sometimes difiicult toraise the temperature above 160 C. due to severe foaming. Thisdifficulty can be overcome .by holding the mixture at temperatures of140 to 160 C.

for several hours or by the addition of some heterocyclic amide from aprevious preparation. This same difficulty may be overcome by theaddition of small amounts of lower alcohols, such as n-butyl alcohol,n-amyl alcohol, methyl isobutyl carbinol, etc., which later distill outas the reaction temperature is raised.

The following exampless are given by way of best illustrating thecompounds covered by this invention-and are not to be taken as limitingthe invention in any way.

Example 1 141 gms. ofoleic acid was added to 98 gms. of N- .methylglucamine and heated for 2 hrs. at a reaction temperature of 168 to 184C. During this reaction period 9.5 cc. of water was removed. The producthad an acid number of 10, saponification number of 40 and a hydroxylnumber of 436.

Example 2 166 gms. of erucic acid was added to 97 gms. of N-methylglucamine and the mixture was heated for 50 minutes at a reactiontemperature of 180 to 194 C. The reaction product had an acid number of12.5, saponification number of 41.5 and a hydroxyl number of 426.

Example 3 100 gms. of lauric acid was added to 1101 gms. of N- methylglucamine and the mixture was heated for 1 hr. at a reaction temperatureof 192 to 197 C. The reaction product had an acid number of 7.0, asaponification number of 30 and a hydroxyl number of 485.

Example 4 142 gms. of stearic acid was added to 100 gms. of N- methylglucamine and the mixture was heated for 2% hrs. at a reactiontemperature of 182 to 196 C. yielding 10.5 cc. of water. The reactionproduct had an acid number of 5.8, a saponification number of 29.5 and ahydroxyl number of 348.

Example 5 250 gms. of lauric acid was added to 252 gms. of N-methylglucamine and the mixture was heated for 3 hrs. at a reactiontemperature of 150 to 185 C. during which time 29 cc. of water was givenoff and collected. The reaction product had an acid number of 19.5, asaponification number of 86 and a hydroxyl number of 685. It is to beobserved that the high saponification number and hydroxyl number here isprobably due to the fact that for the first 2% hrs. of the reaction thetemperature range was 150 to 170 C., while the higher tem peraturereaction, 170 to 185 0., was applied for but .6 hour. This accounts forthe fact that less than 2 moles of water was removed.

Example 6 500 gms. of lauric acid was added to 495 gms. of N-methylglucamine and the reaction mixture was heated for 1% hrs. at atemperature of 170 to 193 C. 25 cc. of butanol was added to the mixture,prior to heating, to reduce foaming. 83 cc. of water was eliminated fromthe reaction mass during the heating period. The product had an acidnumber of 7.4, a saponification number of 32.3 and a hydroxyl number of505.

Example 7 705 gms. of oleic acid was added to 495 gms. of N- methylglucamine and the reaction mixture was heated for 3 hrs. at atemperature of 1631 to 202 C. Prior to heating, 50 cc. of butanol wasadded to the reaction mixture to reduce foaming. During the heating, 77cc. of water was eliminated from the reaction mass. The product had anacid number of 5.3, a saponification number of 25.8 and a hydroxylnumber of 394.

Example 8 1001 gms. of lauric acid was added to 990 gms. of N-methylglucamine. Prior to heating this mixture, 50 cc. of butanol and 35 cc.of methyl isobutyl carbinol were added to the reaction mixture to reducefoaming. The reaction mixture was heated for 3% hrs. at a reactiontemperature of 160 to 192 C. During this time 166 cc. of water was givenoil by the reaction mass. The product had an acid number of 6.4, asaponification number of 33.9 and a hydroxyl number of 479.

Example 9 1410 gms. of oleic acid was added to 990 gms. of N-methylglucamine. To reduce foaming, 82.5 gms. of the product of Example 7 wasadded to the reaction mixture. The reaction mixture was heated for 1 /2hrs. at a temperature of 160 to 195 'C., during which time 157 4 cc. ofwater was evolved and collected from the reaction mass. The resultingproduct had an acid number of 6.2, a saponification number of 29, and ahydroxyl number Example 10 172 gms. of tall oil (acid No. 163) and 98gms. of N-methyl glucamine, were reacted at a temperature of 192 to 207C. for 2% hrs. 15 cc. of water was evolved and collected during thereaction. The product was a soft, brown, resinous mass.

Example 12 52 gms. of N-ethyl glucamine and 7:1 gms. of cottonseed oilfatty acids were reacted at a temperature of 180 to 208 C. for 2 /2 hrs.8.5 cc. of water was evolved and collected during the reaction. Theproduct was a very viscous brown liquid.

Example 13 99.5 gms. of N-methyl glucamine and 98 gms. of coco nut fattyacids (average mol. wt. 192) were reacted by first melting the N-methylglucamine and added rapidly to the fatty acids which were preheated toC. The mixture was heated at 184 to 202 C. for 2 hrs. 18 cc. of waterwas collected during the reaction. During the reaction, the reactionmixture was blanketed with nitrogen to assistthe removal of water.

Example 14 1501 gms. of N-methyl glucamine was melted and to it wasadded 1485 gms. of lauric acid which had been preheated to 160 C. Thelauric acid was added gradually over a period of /2 hr. The reactionmixture was held at to 195 C. for 2% hrs. while blanketing withnitrogen. During this time 266 cc. of water was evolved. The reactionproduct was a viscous liquid which analyzed as follows: acid number 5.4,saponification number 27.8 and hydroxyl number 463.

It has been found that the products typified by the preceding examplesare suitable for use as intermediates for the preparation of anhydroglucamines and N-sub' stituted anhydro glucamines. This can beaccomplished by saponification, thus splitting off the amide to formeither the anhydro glucamine or the N-substituted anhydro glucamine.

The compounds of the present invention exhibit valuable properties asnon-corrosive anti-static agents. The method of application comprisesthe preparation of a solution of the desired compound at a concentrationcalculated to yield .3% to 1.0% solids pickup on the weight of thematerial being treated. These compounds can be applied from aqueoussolutions or from suitable aliphatic or aromatic hydrocarbon solvents,etc., with the aid of a coupler if needed. It can be applied from an oilsolution with the aid of a hydrophobic solubilizer or the oil mixturecan be applied as a water emulsion, with the aid of a coupler andemulsifier. Suitable solutions of the compounds may be applied byspraying, pad roll, dye machine, dye bath or by roll applicator and thelike. The following examples are supplied to show the effectiveness ofthe compounds of the present invention as textile anti-static agents.

Example 15 A 1% water solution of the lauric amide of anhydro N-methylglucamine is heated to 60 C. A sample of Example 16 An oil solublemixture is prepared by mixing equal parts of the lauric amide of anhydroN-methyl glucamine and sorbitan monopalmitate. 'I'he sorbitanmonopal-mitate is here used as an emulsifier and coupling agent. Themixture is then added to a light textile grade oil to yield a solutionof 1% solids concentration. This oil solution is then applied to nylonyarn as a lubricating anti-static finish. The treated yarn showsexcellent resistance to static accumulation.

The compounds of the present invention may be applied as anti-staticagents to fibers, staple fibers, felts, cords, threads, yarns,pellicles, filaments, fabrics, and the like. Textiles of either naturalor synthetic origin may be so treated. Thus cellulosic fibers,regenerated protein fibers, polyacrylic fibers, polyester fibers, wool,silk, bast fibers, glass and the like are amenable to the use of thecompounds of the present invention as anti-static agents.

It will be understood that the embodiments of the invention described inthe specification and illustrated by the examples are only illustrativeof the compounds and the manner in which they are produced. Variousmodifications can be made without departing from the principles of theinvention.

What is claimed is:

1. Heterocyclic amides of the formula The empirical formula (C H (OH)represents the heterocyclic residue of a hexane pentol from which onemole of water has been removed which residue is joined with the Nthrough a carbon linkage R is a monovalent hydrocarbon radical R is thehydrocarbon residue of a carboxylic acid having from 2 to 25 carbonatoms.

2. As a new composition of matter, an N-lower a1kyl-N-anhydrosorbitylamide of an aliphatic carboxylic acid that containsfrom eight to eighteen carbon atoms, said composition having the formula0 RC ON-CH2CHOHCHCHOHCHOHlHg in which R is an alkyl group of one to fourcarbon atoms and R is a member of the class consisting of alkyl andalkenyl groups of seven to seventeen carbons.

3. As a new composition of matter, an N-lower alkyl-N-anhydrosorbitylamide of a fatty acid that contains from eight toeighteen carbon atoms, said comoposition having the formula in which Ris an alkyl group of one to four carbon atoms and R is a residue of afatty acid, said residue containing from seven to seventeen carbonatoms.

4. As a new composition of matter, an N-methyl- N- anhydrosorbitylamideof a 'fatty acid that contains from eight to eighteen carbon atoms, saidcomposition having the formula O ROOIE-CHZCHOHiHGHOHCHOHlHB in which Ris a residue of a fatty acid, said residue containing from seven toseventeen carbon atoms.

5. As a new composition of matter, N-methyl-N-anhydrosorbityllauramidehaving the formula 6. As a new-composition of matter,N-methyl-N-anhydrosorbitylamide of cocoanut oil fatty acids having theformula 0 RCON-CHzCHOHHCHOHCHOH H2 in which R is the residue of cocoanutoil fatty acids.

7. A method for the preparation of N-lower-alkyl-N- anhydrosorbitylamideof an aliphatic carboxylic acid having the formula 0 RC ON-OHnCHOHHCHOHOHOHAH 0 RCOIIT-CH OHOHOHCHOHCHOHlH1 in which R is an alkyl groupof one to four carbon atoms and R is a residue of a fatty acid, saidresidue containing from seven to seventeen carbon atoms which comprisesheating an N-lower alkylglucamine with a fatty acid containing fromeight to eighteen carbon atoms until substantially exactly two molecularequivalents of water are evolved.

References Cited in the file of this patent UNITED STATES PATENTS1,985,424 Piggott Dec. 25, 1934 2,653,932 Schwartz Sept. 29, 1953 2,703798 Schwartz Mar. 8, 1955

1. HETEROCYCLIC AMIDES OF THE FORMULA